Repozytorium

2,7-disubstituted proton sponges as borderline systems for investigating barrier-free intramolecular hydrogen bonds. Protonated 2,7-bis(trimethylsilyl)- and 2,7-di(hydroxymethyl)-1,8-bis(dimethylamino)naphthalenes.

Autorzy

A. V. Degtyarev

O. V. Ryabtsova

Alexander F. Pozharskii

Valery A. Ozeryanskii

Z. A. Starikova

Lucjan Sobczyk

Aleksander Filarowski

Rok wydania

2008

Czasopismo

Tetrahedron

Numer woluminu

64

Strony

6209-6214

DOI

10.1016/j.tet.2008.05.00

Kolekcja

Naukowa

Język

Angielski

Typ publikacji

Artykuł

Streszczenie

Protonated 2,7-bis(trimethylsilyl)- and 2,7-di(hydroxymethyl)-1,8-bis(dimethylamino)naphthalenes have been prepared and studied by a combination of X-ray crystallography at room and low temperatures, IR and NMR spectroscopic techniques in conjunction with quantum-chemical calculations. It was demonstrated that the intramolecular [NHN] + hydrogen bond in the 2,7-bis(trimethylsilyl) system, being sterically compressed, is the shortest among all known aromatic diamine systems. Nevertheless, as it is evidenced by the primary 1 H/ 2 H isotope effect, IR spectra and MP2 calculations, a double minimum potential for the proton motion still exists with a very low barrier estimated to be about 0.7kcal/mol. An influence of a counter-anion on the NH proton involving the spatially hindered H-bond is also considered.

Słowa kluczowe

Sterically modified proton sponges, Intramolecular hydrogen bond, Proton transfer, Molecular structure

Adres publiczny

https://doi.org/ 10.1016/j.tet.2008.05.00

Strona internetowa wydawcy

http://www.elsevier.com

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